CN1711292A - Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof - Google Patents
Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof Download PDFInfo
- Publication number
- CN1711292A CN1711292A CNA2003801033661A CN200380103366A CN1711292A CN 1711292 A CN1711292 A CN 1711292A CN A2003801033661 A CNA2003801033661 A CN A2003801033661A CN 200380103366 A CN200380103366 A CN 200380103366A CN 1711292 A CN1711292 A CN 1711292A
- Authority
- CN
- China
- Prior art keywords
- divinyl
- multipolymer
- equal
- ethene
- catalyst system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 143
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000005977 Ethylene Substances 0.000 title claims abstract description 5
- 229920001577 copolymer Polymers 0.000 title abstract description 8
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 5
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 49
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 5
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 21
- 229910052779 Neodymium Inorganic materials 0.000 claims description 18
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 lanthanide metals Chemical class 0.000 claims description 12
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 239000003426 co-catalyst Substances 0.000 abstract 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract 1
- 238000005755 formation reaction Methods 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 238000007334 copolymerization reaction Methods 0.000 description 15
- 230000000536 complexating effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000001542 size-exclusion chromatography Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical class CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates, in particular, to ethylene and butadiene copolymers and to a catalytic system which can be used for the synthesis of said copolymers. The inventive copolymers comprise a molar ratio of units derived from butatdiene which is greater than or equal to 8 %, said units comprising trans-1,2 cyclohexane chain formations, and have an average molecular mass Mn which is greater than or equal to 40 000 g/mol. According to the invention, the catalytic system consists of (i) an organometallic complex which is represented by either formula A or B, wherein: Ln represents a lanthanide and X represents a halogen. In formula A, two ligand molecules Cp1 and Cp2, which are each formed by a fluorenyl group, are linked to Ln. In formula B, a ligand molecule is linked to Ln, said molecule being formed by two fluorenyl groups Cp1 and Cp2 which are interconnected by a bridge P having formula MR2, wherein M is an element from column IVA and R is an alkyl with between 1 and 20 carbon atoms. The catalytic system also consists of (ii) a co-catalyst belonging to the group comprising a magnesium alkyl, a lithium alkyl, an aluminium alkyl, a Grignard reagent or a mixture of said components. Said catalytic system is such that the molar ratio (co-catalyst/organometallic complex) lies between 1 and 8.
Description
The present invention relates to the multipolymer of ethene and divinyl, be used for the catalyst system of synthetic these multipolymers and the method for synthesizing these multipolymers by this catalyst system.
Known use is based on the catalyst system of the halo title complex of transition metal such as titanium, and it is used to make ethene and conjugated diolefin copolymer.
Japanese patent application JP-A-10 237 131, JP-A-09 316 118 and JP-A-11 171 930 disclose the multipolymer of ethene and divinyl, wherein can adopt cis-1,4, anti-form-1,4 ,-1,2, the form of cis-cyclopentyl and trans-cyclopentyl key is inserted divinyl.Obtain these multipolymers by the catalyst system that comprises dimetylsilyl (pentamethyl-cyclopentadienyl) (tert-butylamides) titanium dichloride and methylaluminoxane.
Also known use based on the catalyst system of halo lanthanide complex so that ethene and conjugated diolefin copolymer.
Especially, patent specification EP-A-1 092 731 and article " Macromolecules; vol.33; no.23; pp.8521-8523 (2000) " explanation in its copolymerization test will be selected from the promotor of alkyl magnesium, lithium alkylide, aluminum alkyls, Grignard reagent or these component mixtures, combine with organometallic complex by one of following general formula A and B expression, to have the multipolymer of gratifying polymerization yield synthesizing ethylene and conjugated diene:
-wherein Ln represents that ordination number can be the lanthanide metals of 57-71,
-wherein X can represent it is the halogen of chlorine, fluorine, bromine or iodine,
-wherein in general formula A, identical or different with two by replacing or do not replace the ligand molecular Cp that fluorenyl is formed
1And Cp
2Ln is connected with metal,
Wherein in Formula B, will be by two cyclopentadienyls or fluorenyl Cp
1And Cp
2The ligand molecular of forming is connected described Cp with metal Ln
1And Cp
2Be to replace or unsubstituted and by satisfying formula M R
2Bridging P connect, wherein M be the element on Mendeleev chart IVa hurdle and wherein R be the alkyl that contains 1-20 carbon atom,
Wherein (promotor/organometallic complex) ratio equals 20.
As if in described document EP-A-1 092 731, the multipolymer that obtains comprises the unit that derives from divinyl, according to the catalyst system that uses, this unit can comprise or can not comprise that form is an anti-form-1, the key of 2 hexanaphthenes.In addition, for the multipolymer that obtains in the document, when its unitary molar content that derives from divinyl is at least 8%, show below number-average molecular weight Mn: this lower number-average molecular weight Mn is measured as by polystyrene equivalent size exclusion chromatography technology (the SEC technology of describing in appendix) and always is significantly less than 40,000g/mol.
An object of the present invention is to propose a kind of special ethylene and butadienecopolymer synthetic catalyst system of can be used for, the unitary molar content that wherein derives from divinyl is at least 8%, contain anti-form-1 in described unit, 2 hexanaphthene keys and molecular weight Mn are greater than the molecular weight of the multipolymer that obtains in document EP-A-1 092 731.
Be surprised to find as the applicant, reach described purpose and be in the above-mentioned catalyst system of described document EP-A-1 092731, to pass through to select following content:
(i) two ligand molecular Cp
1And Cp
2, this ligand molecular can be identical or different, is connected with metal Ln and each is formed by replacing or do not replace fluorenyl, condition is that described organometallic complex meets described general formula A, or ligand molecular is connected with described metal Ln and by two fluorenyl Cp
1And Cp
2Form this fluorenyl Cp
1And Cp
2Can be identical or different, be that replace or unsubstituted and by satisfying formula M R
2Bridging P connect, wherein M is that the element and the R on IVa hurdle are the alkyl that contains 1～20 carbon atom, condition be this organometallic complex general molecular formula B and
(ii) particularly, (promotor/organometallic complex) mol ratio is 1～8.
Can obtain the multipolymer of ethene and divinyl with gratifying polymerization yield, described multipolymer derives from the unit of divinyl and comprises anti-form-1,2 hexanaphthene keys, the described unitary molar content that derives from divinyl more than or equal to 8% and according to the molecular weight Mn of the polystyrene equivalent SEC commercial measurement of stipulating in the appendix more than or equal to 40,000g/mol.
Known to the applicant, for the multipolymer of ethene and divinyl, never obtain anti-form-1 up to now, 2 hexanaphthene keys, the unitary molar content that derives from divinyl be at least 8% and these of the molecular weight Mn that improves in conjunction with feature.
It should be noted that by the ethene that obtains based on the halo lanthanide complex and demonstrate this unitary molar content that derives from divinyl and the high molecular Mn of butadienecopolymer be not conspicuous.In fact, to well known to a person skilled in the art (referring to above-mentioned article " Macromolecules; vol.33; no.23; pp.8521-8523 (2000) ") molecular weight Mn high more (or low more) by the multipolymer of such catalyst system acquisition, the unitary molar content that derives from divinyl low more (or high more respectively).
Also noticeablely be to use specific fluorenyl in the multipolymer that obtains, to obtain anti-form-1,2 hexanaphthene keys, and ultralow (promotor/organometallic complex) mol ratio makes its unitary content that might obtain deriving from divinyl be at least 8% multipolymer that demonstrates high molecular Mn simultaneously.
Preferably, multipolymer according to the present invention comprises more than or equal to 1% He its unit that derives from divinyl, even more preferably, is anti-form-1 more than or equal to the form of 5% mole fraction, the key of 2 hexanaphthenes.Can articles of reference " by
1H and
13The research of the ethene that C NMR carries out/butadienecopolymer microstructure, Llauro M.F., Monnet C., Barbotin F., Monteil V., Spitz R., Boisson C., Marcomolecules 2001,34,6304-6311 " in about
1H and
13The detailed description of C NMR,
1H NMR and
13C NMR is used for the application to measure these anti-form-1s the ad hoc approach of 2 hexanaphthene key mole fractions.
Advantageously, preferably equal or equal 2 substantially by use, for example in 1 to 3 scope (promotor/organometallic complex) mol ratio, make mass M n according to ethene of the present invention and butadienecopolymer more than or equal to 50,000g/mol, even more than or equal to 80,000g/mol.
More advantageously, according to the mass M n of multipolymer of the present invention more than or equal to 100,000g/mol, even more than or equal to 200,000g/mol or 300,000g/mol.
Equally advantageously, according to the unitary molar content that derives from divinyl of multipolymer of the present invention further more than or equal to 10%, even more than or equal to 15%.
It should be noted that can be advantageously in conjunction with following feature according to multipolymer of the present invention: on the one hand, molecular weight Mn is more than or equal to 40,000g/mol and, on the other hand, the unitary molar content that derives from divinyl may be more than or equal to 20% with even more than or equal to 30% more than or equal to 15%.
Also it should be noted that can be advantageously in conjunction with following feature according to multipolymer of the present invention: on the one hand, molecular weight Mn is more than or equal to 100,000g/mol and, on the other hand, described unitary molar content is more than or equal to 15%, even more than or equal to 20%.
Also it should be noted that can be advantageously in conjunction with following feature according to multipolymer of the present invention: on the one hand, molecular weight Mn is more than or equal to 200,000g/mol and, on the other hand, described unitary molar content is more than or equal to 15%, even more than or equal to 20%.
Also it should be noted that can be advantageously in conjunction with following feature according to multipolymer of the present invention: on the one hand, molecular weight Mn is more than or equal to 300,000g/mol and, on the other hand, described unitary molar content is more than or equal to 15%, even more than or equal to 20%.
According to another feature of the present invention, according to the heterogeneity index Ip of multipolymer of the present invention less than 3.5.Preferably, the Ip index of this multipolymer be less than or equal to 3 or, even more preferably, this Ip index is less than or equal to 2.5.Follow the example of molecular weight Mn, use size exclusion chromatography (the SEC technology of in appendix, describing) to measure heterogeneity index Ip in this application.
Glass transition temperature Tg according to multipolymer of the present invention preferably is lower than-10 ℃.More accurately, the temperature T g of multipolymer for example can be-20 ℃～-50 ℃.
Use this temperature T of " Setaram DSC 131 " apparatus measures g by " DSC " (dsc) in this application.The temperature program(me) of using is corresponding to rise to 150 ℃ from-120 ℃ under the speed of 10 ℃/min.
Multipolymer of the present invention shows below microstructure features:
Anti-form-1,4; 1,2 (vinyl) and anti-form-1,2 hexanaphthene keys.
More accurately, if the organometallic complex that uses is the not bridge joint title complex that satisfies described general formula A and comprise two fluorenyls, then described title complex preferably satisfies structural formula (C
13H
9)
2NdCl, by anti-form-1,4 keys insert copolymer chain (unit that promptly derives from divinyl comprises greater than 50%, is typically greater than the anti-form-1 of 70% mole fraction, 4 keys) with most of divinyl.
Yet if according to the preferred embodiments of the invention, the organometallic complex of use is the bridge joint title complex that satisfies this Formula B and comprise two fluorenyls, and described title complex preferably satisfies structural formula [(C
13H
8)
2SiMe
2] NdCl, multipolymer according to the present invention makes its unit that derives from divinyl comprise molar ratio more than or equal to 10%, advantageously more than or equal to 20% He, even is anti-form-1 more than or equal to 50% form more advantageously, the key of 2 hexanaphthenes.
The catalyst system that is used to obtain described multipolymer according to the present invention comprises:
(i) the described organometallic complex of representing by one of following general formula A and B:
Wherein Ln represents that ordination number can be 57～71 lanthanide metals, preferred neodymium
Wherein X represents it can is the halogen of chlorine, fluorine, bromine or iodine,
Wherein in general formula A, two identical or different each are by replacing or do not replace the ligand molecular Cp that fluorenyl is formed
1, Cp
2Be connected with Ln,
Wherein in Formula B, by two identical or different fluorenyl Cp
1And Cp
2The ligand molecular of forming is connected this fluorenyl Cp with Ln
1And Cp
2Be to replace or unsubstituted and by satisfying formula M R
2Bridging P connect, wherein M is the element on IVa hurdle, preferred silicon, and R be contain 1～20 carbon atom alkyl and
The promotor that (ii) belongs to alkyl magnesium, lithium alkylide, aluminum alkyls, Grignard reagent or these component mixtures,
And it is 1～8 that this catalyst system according to the present invention makes (promotor/organometallic complex) mol ratio.
Preferably, described (promotor/organometallic complex) mol ratio is in 1～3 scope, since be used for synthetic multipolymer with following two kinds of features: have more than or equal to 100 the molecular weight Mn of 000g/mol and more than or equal to 8% the unitary molar content that derives from divinyl.
Preferred embodiment according to embodiments of the present invention, Cp
1And Cp
2Each include identical not replacement fluorenyl.
If general formula A is suitable for, Cp
1And Cp
2Each by structural formula C
13H
9Fluorenyl form, and organometallic complex satisfies structural formula (C
13H
9)
2NdCl.
If Formula B is suitable for, Cp
1And Cp
2Each by structural formula C
13H
8Fluorenyl form, and organometallic complex satisfies structural formula [(C
13H
8)
2SiMe
2] NdCl.
Generally speaking, if Cp
1=Cp
2=Cp, by following mode prepare satisfy described general formula A according to not bridge joint organometallic complex of the present invention:
-in step (1), react to obtain lithium salts, then by making hydrogenation ligand molecular and the lithium alkylide represented by structural formula HCp
-in step (2), by in complexing solvent, make described salt with by general formula LnX
3The anhydrous trihalid reaction of the lanthanon of expression, wherein X represents to be the halogen of chlorine, fluorine, bromine or iodine, then
-in step (3), by evaporating described complexing solvent, subsequently in non-complexing solvent, the product of extraction acquisition when second step finishes and randomly,
-in step (4), the product of extraction when finishing by the described third step of crystallization is to obtain not have fully the described organometallic complex of general formula A of described complexing solvent.
Equally generally speaking, if Cp
1=Cp
2=Cp, by following mode prepare satisfy described Formula B according to bridge joint organometallic complex of the present invention:
-in step (1a), react to obtain lithium compound, then by making hydrogenation ligand molecular and the lithium alkylide represented by structural formula HCp
-in step (1b), by making lithium compound and the formula M R that obtains in the step (1a) in complexing solvent
2The dihalide of described bridge, general formula SiMe for example
2Cl
2(wherein Me is a methyl) reaction is to obtain formula M R
2Cp
2Compound, then
-in step (1c), react to obtain formula M R by in non-complexing solvent, making the compound and the lithium alkylide that obtain in the step (1b)
2Cp
2Li
2Lithium salts, then
-in step (2), by in complexing solvent, make described salt with by general formula LnX
3The anhydrous trihalid reaction of the lanthanon of expression, wherein X represents to be the halogen of chlorine, fluorine, bromine or iodine, then
-in step (3), by evaporating described complexing solvent, subsequently in non-complexing solvent, the product of extraction acquisition when second step finishes and randomly,
-in step (4), the product of extraction when finishing by the described third step of crystallization is to obtain not have fully the described organometallic complex of Formula B of described complexing solvent.
In this step (1) and (1a), (1c) in, butyllithium is preferably used as lithium alkylide.
In this step (2) with (1b), tetrahydrofuran (THF) is preferably used as complexing solvent.In addition, two moles of described lithium salts are advantageously with 1 or the described lanthanon trihalid reaction of 2mol.
In this step (3) with (1c), toluene or heptane are preferably used as non-complexing solvent.
As for described promotor, under its situation about being made up of aluminum alkyls and alkyllithium compositions, these two kinds of components are present in the described mixture with stoichiometry or near stoichiometric quantity, to reach gratifying catalytic activity.
In this promotor, butyl octyl magnesium is advantageously used for alkyl magnesium, and butyllithium is as lithium alkylide, and diisobutylaluminium hydride is used as Grignard reagent as aluminum alkyls and butyl magnesium chloride.
Described promotor preferably belongs to butyl octyl magnesium and butyl magnesium chloride, even more preferably, described promotor is a butyl octyl magnesium.
Synthetic method according to multipolymer of the present invention is included under ethene and the divinyl existence, in as the hydrocarbon solvent of toluene and under-20 ℃～120 ℃ temperature, according to the suspension of catalyst system of the present invention or the reaction in the solution.
In reactor, carry out this reaction under the variable pressure of preferred 3 crust-50 crust and preferred 20 ℃-90 ℃ temperature.
Lanthanon concentration is advantageously less than 0.3mmol/l in the reaction medium.And the mole fraction of divinyl advantageously is 5%-80% in this reaction medium.
When the following description of the several embodiment that read embodiment of the present invention, better understand above-mentioned feature of the present invention and further feature, provide this description by non-limitative illustration.
-under argon gas, carry out all following embodiment and in advance by with the reaction of sodium, and subsequently by distillation or adopt 3_ molecular sieve dry employed solvent under argon gas stream.
-use
1H and
13The microstructure of every kind of multipolymer that C NMR technical measurement obtains in these embodiments.For this purpose, " BRUKER DRX 400 " spectrometer is used under the frequency of 400MHz
1Under the frequency of H and 100.6MHz
13C NMR.Can articles of reference " by
1H and
13The research of the ethene of C NMR/butadienecopolymer microstructure, Marcomolecules2001,34,6304-6311 " in about being used for these of embodiment
1H NMR and
13The detailed description of C NMR.
Copolymerization test-" contrast " and the present invention of root a tree name of first series:
Use the contrast catalyst system and carry out these tests according to catalyst system of the present invention, comprise the identical organometallic complex that comprises fluorenyl according to of the present invention on the one hand, on the other hand, comprise according to various promotors of the present invention but that have variation (promotor/organometallic complex) mol ratio.
1) organometallic complex of Shi Yonging:
The utilization structure formula is [(C
13H
8)
2SiMe
2] chlorine (μ-dimetylsilyl) two (the η 5-fluorenyl) neodymium of NdCl, and prepare this title complex in the following way.
A) structural formula isMe
2Si (C
13H
9)
2 Compound synthetic:
SiMe with 6.5mmol
2Cl
2Join the C of 13mmol
13H
9Li is (by fluorenes (C
13H
10) obtain with butyllithium (BuLi) reaction) and 100mL THF solution in, it is cooled to-20 ℃.After rising to room temperature, stirred orange solution 15 hours.Evaporate THF and absorption of residual excess in toluene.Leach salt (LiCl), then evaporated filtrate.Obtain orange solids, wash this orange solids by a little amount of heptane simultaneously at refrigerative.To distil in the vacuum of fluorenes under 85 ℃ of any remnants and separate from product, causing structural formula be Me
2Si (C
13H
9)
2The separation of compound.
The ultimate analysis of this compound shows:
%C=84.63, %H=5.98 (%C=86.55 and %H=6.22 in theory).
By to observed peak group sampling record, (CDCl under 300MHz
3) by
1H NMR characterizes this compound (numerical value of δ (ppm), its integration is corresponding to the proton number):
-for (SiMe
2, 6H) 0.59ppm; For (CH-(C
13H
9), 2H) 4.21ppm;
For (4H) 7.23ppm/ for (4H) 7.32ppm/ for (4H) 7.47ppm/ for (4H) 7.83ppm (CH=(C
13H
9), 16H).
B) structural formula isMe
2Si (C
13H
8)
2Li
2 Salt synthetic:
It is Me that the BuLi solution of 8mmol is joined the 4mmol structural formula
2Si (C
13H
9)
2The 100mL toluene solution of described compound in, it is cooled to-20 ℃.After rising to room temperature, the red solution that obtains was stirred 15 hours and followed stirring and refluxing subsequently 3 hours.Make the yellow solid precipitation.Evaporation toluene and with the solid that obtains at refrigerative simultaneously by a little amount of heptane washing and dry.Thereby collecting corresponding to structural formula is Me
2Si (C
13H
8)
2Li
2The yellow solid (yield is 85%) of salt.
C) structural formula is[(C
13H
8)
2SiMe
2] NdCl
Organometallic complex synthetic:
NdCl with 3.6mmol
3Follow among the THF that is stirred in 75mL and refluxed 12 hours.Adding described structural formula then is Me
2Si (C
13H
8)
2Li
2Salt (3.9mmol) solution.Then the dark brown solution that obtains is stirred and spend the night and backflow THF.Evaporating solvent and in toluene the absorption of residual excess.Leach the salt (LiCl) of formation.Evaporation toluene is to obtain corresponding to structural formula [(C
13H
8)
2SiMe
2] brown solid of organometallic complex of NdCl.
2) according to copolymerization test 1 and 2 of the present invention:
Carry out two copolymerization tests, each test comprises that in comprising 300mL reaction of toluene device introducing concrete quality quantity is described the organometallic complex [(C of x (mg)
13H
8)
2SiMe
2] NdCl, have the ethene-divinyl mixture of the divinyl of variable mole fraction y (%) and the promotor of forming by butyl octyl magnesium (BOMAG).
During copolymerization, the internal pressure in the reactor is remained on about 4 crust and temperature of reactor is remained on 80 ℃.
Afterwards through reaction times t (min.), stop copolymerization by cooling and degassing reactor, obtain multipolymer by precipitation in methyl alcohol then.After drying, the acquisition quality is the multipolymer of m (g).
Use promotor to equal (promotor/neodymium) mol ratio of 2.
Ethene and butadienecopolymer to every kind of acquisition are measured following performance:
Derive from the unitary molar content τ (%) of divinyl in the-multipolymer,
The glass transition temperature Tg of-this multipolymer,
-insert the butadiene unit in the copolymer chain microstructure and
The molecular weight Mn of-this multipolymer and heterogeneity index Ip.
Following table 1 comprises the data that relate to each copolymerization test and relate to every kind of synthetic multipolymer.
Table 1:
| Test | ??x(mg) | Promotor and (promotor/neodymium) ratio | ??m(g) | ??t(min) | Divinyl in y (%) monomer | |
| ??No.1 | ??39.5 | ??BOMAG(2/1) | ??12.7 | ??420 | ??20 | |
| ??No.2 | ??33.6 | ??BOMAG(2/1) | ??9.2 | ??180 | ??30 | |
| Test | Divinyl in τ (%) multipolymer | ??Tg(℃) | Divinyl inserts | ??Mn? ? ??(g/mol)/Ip | ||
| ??％1，2 | The % anti-form-1,4 | The % anti-form-1,2 hexanaphthenes | ||||
| ??No.1 | ??13.1 | ??-31.2 | ??27.2 | ??20.4 | ??52.4 | ??147,500/3.1 |
| ??No.2 | ??15.0 | ??-34.0 | ??22.9 | ??25.8 | ??51.3 | ??127,700/3.0 |
These results show the catalyst system according to these tests 1 and 2, its feature especially is the use of fluorenyl in the organometallic complex and less than (promotor/neodymium) mol ratio aspect of 8, make it can obtain the multipolymer of ethene and divinyl, this multipolymer derives from the unitary molar content of divinyl greater than 10%, anti-form-1 in these unit, the mole fraction of 2 hexanaphthene keys is greater than 50%, and molecular weight Mn is greater than 100, and 000g/mol and Ip index are less than 3.5.
3) contrast copolymerization test 3 and 4:
Use the methods identical, adopt identical organometallic complex to carry out two simultaneous tests 3 and 4, distinguish and be that (promotor/neodymium) mol ratio of selecting equals 20 with test 1 and 2.
For test 3, use the promotor of forming by butyl magnesium chloride (BuMgCl), and, use butyl octyl magnesium (BOMAG) for test 4.
Follow the embodiment of table 1, following table 2 comprises the data that relate to each copolymerization test and relate to every kind of synthetic multipolymer.
Table 2:
| Test | ??x(mg) | Promotor and (promotor/neodymium) ratio | ??m(g) | ??t(min) | Divinyl in y (%) monomer | |
| ??No.3 | ??23.1 | ??BuMgCl(20/1) | ??4.2 | ??60 | ??20 | |
| ??No.4 | ??39.7 | ??BOMAG(20/1) | ??13.2 | ??180 | ??20 | |
| Test | Divinyl in τ (%) multipolymer | ??Tg(℃) | Divinyl inserts | ??Mn? ? ??(g/mol)/Ip | ||
| ??％1，2 | The % anti-form-1,4 | The % anti-form-1,2 hexanaphthenes | ||||
| ??No.3 | ??11.8 | Do not measure | ??19.4 | ??23.0 | ??57.6 | ??10,000/1.2 |
| ??No.4 | ??11.0 | ??-28.5 | ??21.8 | ??24.6 | ??53.5 | ??7,800/1.5 |
These results show the catalyst system according to these simultaneous tests 3 and 4, it is characterized in that the use of fluorenyl in the organometallic complex, and not according to (promotor/neodymium) mol ratio aspect that equals 20 of the present invention, make it cannot obtain to have simultaneously the unit and at least 50 that derives from divinyl of at least 8% molar content, (the mass M n of the multipolymer of acquisition is at most 10,000g/mol) for the ethene of the molecular weight Mn of 000g/mol and the multipolymer of divinyl.
4) according to copolymerization test 5-9 of the present invention:
Carry out other five copolymerization test, each test comprises in comprising 200mL reaction of toluene device, adopts to equal (promotor/neodymium) mol ratio of 2 and introduce described the organometallic complex [(C that concrete quality quantity is x (mg)
13H
8)
2SiMe
2] NdCl and the promotor formed by chlorinated butyl octyl group magnesium (BOMAG), introduce the butadiene solution that obtains by dissolving quality z (g) divinyl in 400mL toluene then.
Set up the required internal pressure P of reactor (10 bar pressures of 20 bar pressures of test 5 and test 6～9) and will test 5～8 temperature of reactor and be adjusted to 80 ℃ and will test 9 temperature regulation to 60 ℃ by adding ethene then.
Afterwards through reaction times t (min.), stop copolymerization by cooling and degassing reactor, obtain multipolymer by precipitation in methyl alcohol then.After drying, obtain the multipolymer of quality m (g).
Following table 3 comprises the data that relate to each test 5～9 and relate to every kind of synthetic multipolymer.
Table 3:
| Test | ??x(mg) | Quality of butadiene z (g) | P (crust) | ??T ??(℃) | ??m(g) | ??t(min) | ||
| ??No.5 | ??44.9 | ??16 | ??20 | ??80 | ??21.7 | ??60 | ||
| ??No.6 | ??47.2 | ??18 | ??10 | ??80 | ??15.8 | ??150 | ||
| ??No.7 | ??46.3 | ??7 | ??10 | ??80 | ??11.4 | ??60 | ||
| ??No.8 | ??22.0 | ??8 | ??10 | ??80 | ??5.9 | ??180 | ||
| ??No.9 | ??40.6 | ??10 | ??10 | ??60 | ??15.8 | ??150 | ||
| Test | Divinyl in τ (%) multipolymer | ??Tg(℃) | Divinyl inserts | ??Mn? ? ??(g/mol)/Ip | ||||
| ??％1，2 | The % anti-form-1,4 | The % anti-form-1,2 hexanaphthenes | ||||||
| ??No.5 | ??20.4 | ??-43.8 | ??55.0 | ??25.0 | ??20.0 | ??260,000/1.8 | ||
| ??No.6 | ??30.4 | ??-45.8 | ??53.5 | ??27.8 | ??18.7 | ??70,700/2.0 | ||
| ??No.7 | ??19.7 | ??-42.8 | ??45.5 | ??25.2 | ??29.3 | ??73,200/1.9 | ||
| ??No.8 | ??20.0 | ??-43.2 | ??44.5 | ??26.7 | ??28.8 | ??378,600/2.8 | ||
| ??No.9 | ??23.6 | ??-47.6 | ??57.0 | ??22.7 | ??20.3 | ??801,450/1.9 | ||
These results show the catalyst system according to these tests 5～9, its feature especially is the use of fluorenyl in the organometallic complex, equal (promotor/neodymium) mol ratio of 2, and more than or equal to pressure aspect in the reactor of 10 crust, make it can obtain to have molar content greater than 15% the unit that derives from divinyl, mole fraction is greater than 15% anti-form-1,2 hexanaphthene keys in these unit, molecular weight Mn is greater than 50, the ethene of 000g/mol and the multipolymer of divinyl.
It should be noted that the multipolymer that obtains in 5,8 and 9 in test advantageously has greater than 200,000g/mol, even up to 300, the mass M n of 000g/mol, and less than 3.0 Ip index.
" contrast " of second series its poly-test:
The catalyst system that is used for these " contrasts " test comprises " contrast " organometallic complex that contains fluorenyl on the one hand, on the other hand, comprises according to various promotors of the present invention, that have variation (promotor/organometallic complex) mol ratio.
1) organometallic complex of Shi Yonging:
The utilization structure formula is { [(C
5H
3)
2SiMe
3]
2SiMe
2Chlorine (μ-dimetylsilyl) two (the η 5-trimethyl silyl cyclopentadienyl) neodymium of NdCl, it is prepared as follows.
A) structural formula is[(C
5H
4) SiMe
3]
2SiMe
2 Compound synthetic:
With the structural formula of 16mmol is Li[(C
5H
4) SiMe
3] compound, the Me of 8mmol
2SiCl
2Introduce the Schlenk pipe with 80mL THF.Mixture at room temperature stirred spend the night.Evaporating solvent is also used 40mL heptane absorption of residual excess.Filtering solution and evaporating solvent.The final product that obtains is the viscous oil of described compound said structure formula.
B) structural formula is[(C
5H
3) SiMe
3]
2SiMe
2Li
2 Salt synthetic:
Under 0 ℃, the BuLi of 14mmol is joined in the Schlenk pipe that contains THF solution gradually, it is [(C that this THF solution contains the 7mmol structural formula
5H
4) SiMe
3]
2SiMe
2Described compound.Mixture was at room temperature stirred 6 hours and in THF solution, obtains above-mentioned salt.
C) structural formula is{ [(C
5H
3) SiMe
3]
2SiMe
2NdCl
Organometallic complex synthetic:
In THF, with 4mmolNdCl
3Stirring also refluxes and spends the night.Adding the 4mmol structural formula then in THF is [(C
5H
3)
2SiMe
3]
2SiMe
2Li
2Described salts solution.Then mixture was at room temperature stirred 36 hours.Evaporating solvent and in toluene the absorption of residual excess.Filtering solution makes the product crystallization then under-20 ℃.Obtain this organometallic complex subsequently.
The centesimal system ultimate analysis of this title complex shows the following per-cent of carbon atom and hydrogen atom:
%C=42.88, %H=5.87 (in theory: %C=42.36 and %H=5.92).
By to observed peak group sampling record, (C under 300MHz
6D
6) by
1H NMR characterizes this compound (numerical value of d (ppm), its integration is corresponding to the proton number):
Observe two groups of peaks by this technology, the integration at every group of peak is corresponding to 3 protons: observe first group of peak and observe the Si (CH that this title complex is all represented at second group of peak at-8.97ppm at 2.13ppm
3)
2Proton.
At last, observe the peak group under-2.99ppm, its integration is corresponding to 18 protons and represent two Si (CH of this title complex
3)
2Substituent proton.
It should be noted that and do not detect corresponding to C
5H
3The peak of proton, may be because the non-constant width in these peaks.
2) " contrast " copolymerization test 10 and 11:
Carry out two " contrast " test earlier, each test comprises in containing 300mL reaction of toluene device, and the structural formula of introducing concrete quality quantity and be x (mg) is { [(C
5H
3) SiMe
3]
2SiMe
2The described organometallic complex of NdCl, ethene-divinyl mixture and promotor with variable divinyl mole fraction y (%), the latter is made up of butyllithium (BuLi) and diisobutylaluminium hydride (DiBAH) and (promotor/neodymium) mol ratio is 20/1.
The internal pressure of reactor is remained on about 4 crust.Between polymerization period, reactor remained on 80 ℃ or 60 ℃ (respectively for test 10 or 11).
Afterwards through reaction times t (min.), stop copolymerization by cooling and degassing reactor, obtain multipolymer by precipitation in methyl alcohol then.After drying, the acquisition quality is the multipolymer of m (g).
Following table 4 comprises the data that relate to each test 10 and 11 and relate to every kind of synthetic multipolymer.
Table 4:
| Test | ?x(mg) | (BuLi/DiBAH/ neodymium) ratio | P (crust) | ??T ??(℃) | ??m(g) | ??t(min) |
| ??No.10 | ?30 | ??10/10/1 | ??4 | ??80 | ??4.8 | ??120 |
| ??No.11 | ?31 | ??10/10/1 | ??4 | ??60 | ??2.1 | ??60 |
| Test | Y (%) monomer | In τ (%) multipolymer | Divinyl inserts | ??Mn | ||
| In divinyl | Divinyl | ??％1，2 | The % anti-form-1,4 | ??(g/mol)/Ip | |
| ??No.10 | ??43.0 | ??41.0 | ??2.5 | ??97.5 | ??6,900/2.2 |
| ??No.11 | ??40.0 | ??37.5 | ??2.5 | ??97.5 | ??10,530/1.8 |
These results show the catalyst system according to these " contrasts " test 10 and 11, it demonstrates feature aspect use of cyclopentadienyl especially in organometallic complex, make it cannot obtain containing anti-form-1, the ethene of 2 hexanaphthene keys and the multipolymer of divinyl.
In addition, use to equal (promotor/neodymium) mol ratio of 20 and make these multipolymers to obtain at least 40 the molecular weight Mn of 000g/mol.
3) " contrast " copolymerization test 12:
Use the methods identical with above-mentioned " contrast " test 11, difference is: this test promotor that 12 catalyst system is characterised in that use only is made up of butyllithium with equal 2 according to (promotor/neodymium) of the present invention ratio aspect.
Following table 5 comprises the data that relate to each test 12 and relate to every kind of synthetic multipolymer.
Table 5:
| Test | ?x(mg) | (promotor/neodymium) ratio | P (crust) | ??T ??(℃) | ??m(g) | ??t(min) | |
| ??No.12 | ?55 | ??2/1 | ??4 | ??60 | ??2.3 | ??240 | |
| Test | Divinyl in y (%) monomer | Divinyl in τ (%) multipolymer | Divinyl inserts | ??Mn ??(g/mol)/Ip | |||
| ??％1，2 | The % anti-form-1,4 | ||||||
| ??No.12 | ?40.0 | ??40.2 | ??2.3 | ??97.7 | ??44,600/1.8 | ||
These results show because the feature aspect the use of its cyclopentadienyl in organometallic complex, although test " contrast " catalyst system of 12 equal 2 aspect (promotor/neodymium) of the present invention mol ratio, demonstrate feature, but also make it cannot obtain containing anti-form-1, the ethene of 2 hexanaphthene keys and the multipolymer of divinyl.
Appendix:
Measure the molecular weight distribution of the multipolymer that obtains by size exclusion chromatography (SEC).
A) measuring principle:
SEC (size exclusion chromatography) makes it separate macromole by its size physicsization ground at solvent swelling state in the pillar of being filled by the porous stationary phase.Separate macromole by its hydrodynamic volume, maximum wash-out at first comes out.Although be not absolute method, SEC can carry out the evaluation of molecular weight distribution.
Use by polystyrene (number-average molecular weight Mn is 580g/mol-3,150,000g/mol) the commercial criterion thing of Zu Chenging can be measured different mass M n and Mw and calculate heterogeneity index (Ip=Mw/Mn).
More accurately, the polystyrene sample of use has following mass M n (in g/mol): 580-1,700-2,960-28,500-66,000-170,600-526,000-1,290,000-3,150,000.
B) preparation of polymkeric substance:
Before analyzing, polymer samples is not carried out any specific processing.It simply is dissolved in the concentration of tetrahydrofuran (THF) to about 1g/l.
C) SEC analyzes:
The instrument that uses is " WATERS " chromatogram with " 515HPLC " pump and " RI410 " detector.
Eluting solvent is that tetrahydrofuran (THF) and elution rate are 1mL/min.
Use three pillars of a cover, one be " WATERS STYRAGEL HR 4E " pillar and in addition two be " WATERS STYRAGEL HR 5E " pillar.
Column temperature is that 45 ℃ and detector temperature are 40 ℃.
The polymer samples liquor capacity that injects is 50ml.Detector is that " WATERS 2140 " differential refractometer and chromatographic data process software are " WATERS MILLENNIUM " systems.
Claims (23)
1. the multipolymer of ethene and divinyl, comprise molar content more than or equal to 8% the unit that derives from divinyl, described unit comprises that form is an anti-form-1, the key of 2 hexanaphthenes, the number-average molecular weight Mn that it is characterized in that described polymkeric substance is more than or equal to 40,000g/mol.
2. the multipolymer of ethene according to claim 1 and divinyl is characterized in that its number-average molecular weight Mn more than or equal to 100,000g/mol.
3. the multipolymer of ethene according to claim 2 and divinyl is characterized in that its number-average molecular weight Mn more than or equal to 200,000g/mol.
4. the multipolymer of ethene according to claim 3 and divinyl is characterized in that its number-average molecular weight Mn more than or equal to 300,000g/mol.
5. according to the multipolymer of described ethene of aforementioned arbitrary claim and divinyl, it is characterized in that the described unitary molar content of divinyl that derives from is more than or equal to 15%.
6. the multipolymer of ethene according to claim 5 and divinyl is characterized in that the described unitary molar content of divinyl that derives from is more than or equal to 20%.
7. the multipolymer of ethene according to claim 6 and divinyl is characterized in that the described unitary molar content of divinyl that derives from is more than or equal to 30%.
8. according to the multipolymer of described ethene of aforementioned arbitrary claim and divinyl, it is characterized in that the described unit that derives from divinyl comprises that mole fraction is an anti-form-1 more than or equal to 10% form, the key of 2 hexanaphthenes.
9. the multipolymer of ethene according to claim 8 and divinyl is characterized in that the described unit that derives from divinyl comprises that mole fraction is an anti-form-1 more than or equal to 20% form, the key of 2 hexanaphthenes.
10. the multipolymer of ethene according to claim 9 and divinyl is characterized in that the described unit that derives from divinyl comprises that mole fraction is an anti-form-1 more than or equal to 50% form, the key of 2 hexanaphthenes.
11. a catalyst system that is used for synthetic according to described ethene of aforementioned arbitrary claim and butadienecopolymer, described catalyst system comprises:
(i) organometallic complex of representing by one of following general formula A or B:
Wherein Ln represents that ordination number can be the lanthanide metals of 57-71,
Wherein X represents it can is the halogen of chlorine, fluorine, bromine or iodine,
Wherein in general formula A, two identical or different, and fluorenyl forms by replacing or not replacing
Ligand molecular Cp
1And Cp
2Be connected with described metal Ln,
Wherein in Formula B, by two identical or different fluorenyl Cp
1And Cp
2The part of forming
Molecule is connected with described metal Ln, this fluorenyl Cp
1And Cp
2It is replacement or also unsubstituted
And by satisfying formula M R
2Bridging P connect, wherein M is Mendeleev chart IVa
The element on hurdle and R are the alkyl that contains 1～20 carbon atom,
The promotor that (ii) belongs to alkyl magnesium, lithium alkylide, aluminum alkyls, Grignard reagent or these component mixtures,
It is characterized in that (promotor/organometallic complex) mol ratio is 1～8.
12. catalyst system according to claim 11 is characterized in that described (promotor/organometallic complex) mol ratio is 1～3.
13., it is characterized in that representing described organometallic complex by described general formula A according to claim 11 or 12 described catalyst system.
14., it is characterized in that representing described organometallic complex by described Formula B according to claim 11 or 12 described catalyst system.
15. catalyst system according to claim 14 is characterized in that at described formula M R
2Bridging P in the described metal M that comprises be silicon.
16., it is characterized in that in described organometallic complex that described lanthanon Ln is a neodymium according to the arbitrary described catalyst system of claim 11～15.
17., it is characterized in that in described organometallic complex Cp according to the arbitrary described catalyst system of claim 11～16
1And Cp
2Each include identical fluorenyl.
18., it is characterized in that described organometallic complex satisfies structural formula (C according to claim 13 and 17 described catalyst system
13H
9)
2NdCl, wherein Cp
1And Cp
2Each by satisfying structural formula C
13H
9Not replacement fluorenyl form, be used for synthesizing ethylene and butadienecopolymer, the unit that this multipolymer derives from divinyl comprises that mole fraction is greater than 50% anti-form-1,4 keys.
19., it is characterized in that in described organometallic complex Cp according to claim 14 and 17 described catalyst system
1And Cp
2Each by satisfying structural formula C
13H
8Not replacement fluorenyl form.
20., it is characterized in that described organometallic complex satisfies structural formula [(C according to claim 15 and 19 described catalyst system
13H
8)
2SiMe
2] NdCl, being used for the synthetic of ethene and butadienecopolymer, the unit that this multipolymer derives from divinyl comprises that mole fraction is more than or equal to 10% anti-form-1,2 hexanaphthene keys.
21., it is characterized in that described promotor belongs to butyl octyl magnesium or butyl magnesium chloride according to the arbitrary described catalyst system of claim 11～20.
22. synthetic method according to arbitrary described ethene of claim 1～10 and butadienecopolymer, be included in-20 ℃～120 ℃ temperature, ethene and divinyl exist down, in hydrocarbon solvent as toluene, the suspension of catalyst system or the reaction in the solution is characterized in that described catalyst system such as claim 12～22 are defined in each.
23. the synthetic method of ethene according to claim 22 and butadienecopolymer is characterized in that carrying out described reaction under the pressure of 3-50 crust.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0212893 | 2002-10-16 | ||
| FR02/12893 | 2002-10-16 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100042409A Division CN101045770A (en) | 2002-10-16 | 2003-10-13 | Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1711292A true CN1711292A (en) | 2005-12-21 |
| CN100523023C CN100523023C (en) | 2009-08-05 |
Family
ID=32104296
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100042409A Pending CN101045770A (en) | 2002-10-16 | 2003-10-13 | Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers |
| CNB2003801033661A Expired - Lifetime CN100523023C (en) | 2002-10-16 | 2003-10-13 | Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100042409A Pending CN101045770A (en) | 2002-10-16 | 2003-10-13 | Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7094854B2 (en) |
| EP (1) | EP1554321B1 (en) |
| JP (1) | JP5301073B2 (en) |
| KR (1) | KR20050101157A (en) |
| CN (2) | CN101045770A (en) |
| AU (1) | AU2003286138A1 (en) |
| BR (1) | BR0315380A (en) |
| CA (1) | CA2502345A1 (en) |
| RU (1) | RU2312870C2 (en) |
| WO (1) | WO2004035639A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699171A (en) * | 2015-12-08 | 2018-10-23 | 米其林集团总公司 | 1,3- diene and ethylene or simple function or the distant pawl copolymer of α-monoolefine |
| CN108699187A (en) * | 2015-12-08 | 2018-10-23 | 米其林集团总公司 | The simple function or distant pawl copolymer of 1,3- butadiene and ethylene |
| CN111212860A (en) * | 2017-10-19 | 2020-05-29 | 米其林集团总公司 | Block polymers having diene units and monoolefin units |
| CN111819209A (en) * | 2018-03-05 | 2020-10-23 | 株式会社普利司通 | Copolymer, method for producing copolymer, rubber composition, and tire |
Families Citing this family (139)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2893029B1 (en) | 2005-11-09 | 2009-01-16 | Michelin Soc Tech | METALOCENE COMPLEX BOROHYDRIDE OF LANTHANIDE, INCORPORATING CATALYTIC SYSTEM, POLYMERIZATION METHOD USING THE SAME, AND ETHYLENE / BUTADIENE COPOLYMER OBTAINED BY THIS PROCESS |
| FR2893028B1 (en) * | 2005-11-09 | 2008-02-15 | Michelin Soc Tech | METALOCENE COMPLEX BOROHYDRIDE OF LANTHANIDE, INCORPORATING CATALYTIC SYSTEM, POLYMERIZATION METHOD USING THE SAME, AND ETHYLENE / BUTADIENE COPOLYMER OBTAINED BY THIS PROCESS |
| FR2893030B1 (en) * | 2006-10-17 | 2011-04-15 | Michelin Soc Tech | COPOLYMER ETHYLENE / BUTADIENE |
| US8853339B2 (en) | 2009-08-07 | 2014-10-07 | Bridgestone Corporation | Method for producing copolymer |
| FR2957601B1 (en) | 2010-03-18 | 2012-03-16 | Michelin Soc Tech | TIRE AND RUBBER COMPOSITION CONTAINING GRAFT POLYMER |
| FR2962737B1 (en) | 2010-07-13 | 2012-08-17 | Michelin Soc Tech | RUBBER COMPOSITION CONTAINING MODIFIED ELASTOMER, PROCESS FOR PREPARING THE SAME AND PNEUMATIC CONTAINING THE SAME |
| FR2962733B1 (en) | 2010-07-13 | 2012-08-17 | Michelin Soc Tech | POLYMER GRAFTED BY NITROGEN ASSOCIATIVE MOLECULES. |
| FR2962729B1 (en) | 2010-07-13 | 2012-09-21 | Arkema France | CARRIER MOLECULES OF ASSOCIATIVE GROUPS |
| FR2962732B1 (en) | 2010-07-13 | 2012-08-17 | Michelin Soc Tech | POLYMER GRAFTED BY NITROGEN ASSOCIATIVE MOLECULES |
| US9670302B2 (en) | 2010-07-30 | 2017-06-06 | Bridgestone Corporation | Copolymer, rubber composition, crosslinked rubber composition, and tire |
| JP5775873B2 (en) | 2010-07-30 | 2015-09-09 | 株式会社ブリヂストン | Copolymer, rubber composition, crosslinked rubber composition, and tire |
| CN103154058B (en) | 2010-07-30 | 2015-12-16 | 株式会社普利司通 | The multipolymer of conjugated diene compound and non-conjugated alkene, rubber combination and tire |
| JP5764128B2 (en) * | 2010-07-30 | 2015-08-12 | 株式会社ブリヂストン | Copolymer and process for producing the same |
| CN103140521B (en) * | 2010-07-30 | 2015-07-01 | 株式会社普利司通 | Method for controlling chain structure in copolymers |
| JP5918132B2 (en) | 2010-07-30 | 2016-05-18 | 株式会社ブリヂストン | Copolymer of conjugated diene compound and non-conjugated olefin, rubber composition, crosslinked rubber composition, and tire |
| EP2599802B1 (en) | 2010-07-30 | 2015-09-30 | Bridgestone Corporation | Copolymer of conjugated diene compounds and non-conjugated olefins, rubber composition, cross-linked rubber composition, and tyre |
| BR112013019682A2 (en) * | 2011-02-04 | 2016-10-11 | Bridgestone Corp | copolymer, rubber composition, tire side rubber composition, cross-linked rubber composition and tire |
| JP5932224B2 (en) | 2011-02-04 | 2016-06-08 | 株式会社ブリヂストン | Copolymer, rubber composition, crosslinked rubber composition, and tire |
| JP5731217B2 (en) | 2011-02-04 | 2015-06-10 | 株式会社ブリヂストン | Copolymer, rubber composition, crosslinked rubber composition, and tire |
| BR112013019681B1 (en) | 2011-02-04 | 2020-03-24 | Bridgestone Corporation | COPOLYMER OF CONJUGATED DIENOUS AND UNCONJUGATED OLEFINE, RUBBER COMPOSITION, RUBBER COMPOSITION FOR TIRE Tread, Reticulated and TIRE RUBBER COMPOSITION |
| US9469658B2 (en) | 2011-02-05 | 2016-10-18 | Bridgestone Corporation | Lanthanide complex catalyst and polymerization method employing same |
| WO2012117715A1 (en) | 2011-03-01 | 2012-09-07 | 株式会社ブリヂストン | Rubber composition, rubber composition for tire sidewall, crosslinked rubber composition, and tire |
| RU2553474C1 (en) | 2011-06-02 | 2015-06-20 | Бриджстоун Корпорейшн | Copolymer, rubber mixture, cross-linked rubber mixture and tyre |
| EP2810985B1 (en) * | 2012-01-30 | 2017-04-05 | Bridgestone Corporation | Vibration-damping rubber composition, crosslinked vibration-damping rubber composition, and vibration-damping rubber |
| WO2014052957A1 (en) | 2012-09-30 | 2014-04-03 | Bridgestone Corporation | Organometallic catalyst complex and polymerization method employing same |
| WO2014055868A1 (en) | 2012-10-04 | 2014-04-10 | Bridgestone Corporation | Organometallic complex catalyst and polymerization method employing same |
| FR3001223B1 (en) | 2013-01-22 | 2015-03-06 | Michelin & Cie | RUBBER COMPOSITION COMPRISING A HIGHLY SATURATED DIENIC ELASTOMER |
| EP3148937B1 (en) | 2014-05-30 | 2019-09-18 | Bridgestone Corporation | Metallic complex catalyst and polymerization methods employing same |
| RU2690373C2 (en) | 2014-05-31 | 2019-06-03 | Бриджстоун Корпорейшн | Metal complex catalyst, polymerisation methods using same and obtained polymer products |
| FR3023843B1 (en) * | 2014-07-21 | 2016-07-22 | Michelin & Cie | MODIFIED POLYMER ALONG THE CHAIN AND METHOD OF SYNTHESIS |
| FR3037588B1 (en) | 2015-06-19 | 2017-05-19 | Michelin & Cie | THERMOPLASTIC ELASTOMERIC COPOLYMER BASED ON DIENE ELASTOMER AND POLYPROPYLENE, COMPOSITIONS COMPRISING THE SAME, AND PROCESS FOR PREPARING THE SAME |
| CN107921817B (en) * | 2015-07-31 | 2020-02-28 | 倍耐力轮胎股份公司 | High-performance tyre |
| FR3040058B1 (en) | 2015-08-13 | 2019-07-19 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR THE SYNTHESIS OF A POLYMER CARRIER OF A FUNCTIONAL GROUP, PRODUCT THEREOF AND COMPOSITION CONTAINING SAME |
| FR3044010A1 (en) | 2015-11-19 | 2017-05-26 | Michelin & Cie | TIRE TREAD FOR TIRE AIRCRAFT |
| FR3044007B1 (en) | 2015-11-19 | 2017-12-08 | Michelin & Cie | TIRE TREAD FOR TIRE AIRCRAFT |
| FR3044241A1 (en) * | 2015-12-01 | 2017-06-02 | Michelin & Cie | CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE |
| FR3045613B1 (en) * | 2015-12-17 | 2017-12-15 | Michelin & Cie | COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE |
| FR3045612B1 (en) * | 2015-12-17 | 2017-12-15 | Michelin & Cie | COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE |
| FR3045633B1 (en) | 2015-12-22 | 2017-12-15 | Michelin & Cie | PNEUMATIC COMPRISING A RUBBER COMPOSITION COMPRISING A SUBSTITUTED DIENIC ELASTOMER |
| FR3049291B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | SELF-ADHERENT COMPOSITE ELEMENT COMPRISING A BLOCK COPOLYMER |
| FR3049283B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | REINFORCED PRODUCT COMPRISING A SELF-ADHESIVE COMPOSITE REINFORCEMENT COMPRISING A BLOCK COPOLYMER |
| FR3049282B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | REINFORCED PRODUCT COMPRISING A SELF-ADHESIVE COMPOSITE REINFORCEMENT COMPRISING A BLOCK COPOLYMER |
| FR3054220A1 (en) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE |
| FR3054222A1 (en) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR PREPARING A CATALYTIC SYSTEM BASED ON RARE EARTH METALLOCENE |
| FR3054221A1 (en) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE |
| FR3057265A1 (en) | 2016-10-12 | 2018-04-13 | Arkema France | DISSYMETRIC COMPOUNDS CARRYING ASSOCIATIVE GROUPS |
| FR3057264B1 (en) | 2016-10-12 | 2020-05-29 | Arkema France | COMPOUNDS FOR NITROGEN ASSOCIATIVE GROUPS |
| FR3060004B1 (en) | 2016-12-09 | 2019-05-24 | Compagnie Generale Des Etablissements Michelin | ORGANOMETALLIC COMPOUND HAVING IMINOPHOSPHORANE FUNCTION |
| FR3060576A1 (en) | 2016-12-15 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | ELASTOMER DIENIC CARRYING ANTHRACENYL PENDING GROUPS |
| FR3060592A1 (en) | 2016-12-15 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PNEUMATIC COMPRISING A RUBBER COMPOSITION COMPRISING A POLYMER CARRYING A JOINT DIENE GROUP CONNECTED WITH A DIENOPHILE |
| FR3060571A1 (en) | 2016-12-19 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR PREPARING A DIODE MODIFIED ELASTOMER WITH 1,3-DIPOLAR COMPOUND |
| FR3060570A1 (en) | 2016-12-19 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR THE PREPARATION OF A DIODE MODEL ELASTOMER MODIFIED BY A 1,3-DIPOLAR COMPOUND BY REACTIVE EXTRUSION |
| FR3063732A1 (en) | 2017-03-08 | 2018-09-14 | Compagnie Generale Des Etablissements Michelin | PNEUMATIC HAVING A COMPOSITION COMPRISING AN ETHYLENE-RICH ELASTOMER, A PEROXIDE AND A POLYFUNCTIONAL ACRYLATE DERIVATIVE |
| FR3063731A1 (en) | 2017-03-08 | 2018-09-14 | Compagnie Generale Des Etablissements Michelin | PNEUMATIC COMPRISING A COMPOSITION COMPRISING AN ETHYLENE RICH ELASTOMER, A PEROXIDE AND A ZINC ACRYLATE |
| FR3065004A1 (en) | 2017-04-10 | 2018-10-12 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION BASED ON HIGHLY SATURATED DIENE ELASTOMER AND DITHIOSULFATE SALT |
| FR3065005A1 (en) | 2017-04-10 | 2018-10-12 | Compagnie Generale Des Etablissements Michelin | TIRE TREAD FOR PNEUMATIC TIRES BASED ON A HIGHLY SATURATED DIENE ELASTOMER |
| FR3065216A1 (en) | 2017-04-18 | 2018-10-19 | Compagnie Generale Des Etablissements Michelin | CONTINUOUS SYNTHESIS OF COPOLYMER OF ETHYLENE AND BUTADIENE |
| FR3065215A1 (en) | 2017-04-18 | 2018-10-19 | Compagnie Generale Des Etablissements Michelin | CONTINUOUS SYNTHESIS OF COPOLYMER OF ETHYLENE AND BUTADIENE |
| FR3067355A1 (en) | 2017-06-08 | 2018-12-14 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION |
| FR3067354B1 (en) | 2017-06-08 | 2020-10-23 | Centre Nat Rech Scient | FUNCTIONAL COPOLYMER OF ETHYLENE AND 1,3-BUTADIENE |
| FR3067353B1 (en) | 2017-06-08 | 2020-10-23 | Centre Nat Rech Scient | FUNCTIONAL COPOLYMER OF 1,3-DIENE AND OLEFIN |
| EP3645578B1 (en) | 2017-06-28 | 2023-09-06 | Compagnie Générale des Etablissements Michelin | Diene rubber bearing imidazole groups |
| FR3068698A1 (en) | 2017-07-04 | 2019-01-11 | Compagnie Generale Des Etablissements Michelin | POLYMER CONTAINING PARTICULAR FUNCTIONAL PENDING GROUPS IMIDAZOLIDINONE |
| FR3068703A1 (en) | 2017-07-04 | 2019-01-11 | Compagnie Generale Des Etablissements Michelin | COMPOSITION BASED ON AT LEAST ONE PARTICULAR POLYAROMATIC COMPOUND |
| FR3069550A1 (en) | 2017-07-28 | 2019-02-01 | Compagnie Generale Des Etablissements Michelin | EXTENDED ELASTOMER RESIN |
| EP3680259B1 (en) | 2017-09-04 | 2023-08-16 | Bridgestone Corporation | Polymerization catalyst composition, polymer production method, polymer, rubber composition, and tire |
| EP3680265B1 (en) | 2017-09-04 | 2024-01-17 | Bridgestone Corporation | Method for producing copolymer, copolymer, rubber composition, and tire |
| WO2019077232A1 (en) | 2017-10-19 | 2019-04-25 | Compagnie Generale Des Etablissements Michelin | Method for synthesising polymer blocks |
| WO2019077235A1 (en) | 2017-10-19 | 2019-04-25 | Compagnie Generale Des Etablissements Michelin | Block polymers |
| JP7321154B2 (en) | 2017-10-19 | 2023-08-04 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | block polymer |
| CN111356596B (en) | 2017-11-21 | 2022-06-21 | 米其林集团总公司 | Rubber composition |
| EP3713924B1 (en) | 2017-11-21 | 2023-01-04 | Compagnie Générale des Etablissements Michelin | 1,3-dipolar compound comprising an epoxide group |
| EP3713774B1 (en) | 2017-11-21 | 2022-03-09 | Compagnie Générale des Etablissements Michelin | Rubber composition |
| EP3713772B1 (en) | 2017-11-21 | 2022-03-09 | Compagnie Générale des Etablissements Michelin | Diene polymer modified by an epoxide group |
| EP3720700A1 (en) | 2017-12-06 | 2020-10-14 | Compagnie Générale des Etablissements Michelin | Elastomeric laminate |
| WO2019110926A1 (en) | 2017-12-06 | 2019-06-13 | Compagnie Generale Des Etablissements Michelin | Elastomeric laminate |
| FR3078337B1 (en) | 2018-02-27 | 2020-08-07 | Arkema France | USE OF MAGNESIUM OXIDE FOR CROSS-LINKING POLYMERS |
| FR3078336B1 (en) | 2018-02-27 | 2020-09-18 | Arkema France | USE OF MAGNESIUM OXIDE IN THE MANUFACTURE OF TIRES |
| WO2019171679A1 (en) * | 2018-03-05 | 2019-09-12 | 株式会社ブリヂストン | Copolymer, method for producing copolymer, rubber composition and tire |
| FR3085167B1 (en) | 2018-08-23 | 2020-07-31 | Michelin & Cie | PNEUMATICS PROVIDED WITH A COMPOSITION CONSISTING OF AN ELASTOMER RICH IN ETHYLENE, A PEROXIDE AND A SPECIFIC ACRYLATE DERIVATIVE |
| FR3085165B1 (en) | 2018-08-23 | 2020-07-17 | Compagnie Generale Des Etablissements Michelin | TIRE PROVIDED WITH A COMPOSITION COMPRISING AN ETHYLENE-RICH ELASTOMER, A PEROXIDE AND A SPECIFIC ACRYLATE DERIVATIVE |
| FR3085166B1 (en) | 2018-08-23 | 2020-07-17 | Compagnie Generale Des Etablissements Michelin | TIRE PROVIDED WITH A COMPOSITION COMPRISING AN ETHYLENE-RICH ELASTOMER, A PEROXIDE AND A SPECIFIC ACRYLATE DERIVATIVE |
| FR3085683B1 (en) | 2018-09-11 | 2020-10-23 | Michelin & Cie | PNEUMATIC |
| FR3085684B1 (en) | 2018-09-11 | 2021-06-04 | Michelin & Cie | RUBBER COMPOSITION |
| FR3086948B1 (en) | 2018-10-09 | 2020-12-04 | Michelin & Cie | RUBBER COMPOSITION |
| FR3086949B1 (en) | 2018-10-09 | 2020-12-04 | Michelin & Cie | RUBBER COMPOSITION |
| FR3087443B3 (en) | 2018-10-23 | 2020-10-23 | Michelin & Cie | RUBBER COMPOSITION |
| FR3088328B3 (en) | 2018-11-09 | 2020-12-04 | Michelin & Cie | FUNCTIONAL DIENIC ELASTOMER AND RUBBER COMPOSITION |
| FR3090639A3 (en) * | 2018-12-20 | 2020-06-26 | Michelin & Cie | Terpolymers of ethylene, 1,3-butadiene and an aromatic α-monoolefin. |
| FR3090656A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | Tire tread |
| FR3090654A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | Rubber composition |
| FR3090663A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | Tire tread |
| FR3090659A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | Tire tread |
| FR3090661A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | Tire tread |
| FR3104597B1 (en) | 2019-12-16 | 2021-11-12 | Michelin & Cie | RUBBER COMPOSITION |
| FR3104586B1 (en) | 2019-12-17 | 2021-12-03 | Michelin & Cie | Asymmetric diorganomagnesium compound for catalytic system |
| FR3104585B1 (en) | 2019-12-17 | 2021-12-03 | Michelin & Cie | Catalytic system based on a metallocene and a diorganomagnesium |
| FR3104595B1 (en) | 2019-12-17 | 2021-11-12 | Michelin & Cie | PNEUMATIC WITH A TREAD CONTAINING REINFORCING ELEMENTS |
| FR3104584B1 (en) | 2019-12-17 | 2021-12-03 | Michelin & Cie | Asymmetric diorganomagnesium compound |
| FR3108117B1 (en) | 2020-03-10 | 2022-03-25 | Michelin & Cie | Process for manufacturing a rubber composition. |
| FR3111352B1 (en) | 2020-06-11 | 2023-02-10 | Michelin & Cie | RUBBER COMPOSITION WITH IMPROVED RESISTANCE TO AGGRESSION |
| FR3113905B1 (en) | 2020-09-04 | 2022-08-05 | Michelin & Cie | RUBBER COMPOSITION BASED ON HIGHLY SATURATED DIENIQUE ELASTOMER |
| FR3113906B1 (en) | 2020-09-04 | 2022-08-05 | Michelin & Cie | RUBBER COMPOSITION BASED ON HIGHLY SATURATED DIENIQUE ELASTOMER |
| FR3116276B1 (en) | 2020-11-19 | 2023-11-10 | Michelin & Cie | Diorganomagnesium having a diene or olefin chain and amine functional |
| FR3116277A1 (en) | 2020-11-19 | 2022-05-20 | Compagnie Generale Des Etablissements Michelin | Amine functional copolymers with ethylenic and diene blocks |
| FR3116539B1 (en) | 2020-11-24 | 2022-11-25 | Michelin & Cie | Catalytic system based on a rare earth metallocene and a co-catalyst with several carbon magnesium bonds. |
| FR3116538B1 (en) | 2020-11-24 | 2022-11-25 | Michelin & Cie | Co-catalyst comprising several magnesium carbon bonds |
| FR3116535B1 (en) | 2020-11-24 | 2022-11-25 | Michelin & Cie | Telechelic polymers based on ethylene and 1,3-diene |
| FR3116540B1 (en) | 2020-11-24 | 2023-11-03 | Michelin & Cie | Catalytic system based on a rare earth metallocene and a co-catalyst having several carbon magnesium bonds. |
| FR3117404B1 (en) | 2020-12-16 | 2024-02-16 | Michelin & Cie | Elastomeric laminate exhibiting excellent adhesion between a cross-linked, highly saturated diene layer and a vulcanized diene layer |
| FR3118048B1 (en) | 2020-12-22 | 2023-01-13 | Michelin & Cie | Rubber composition comprising rubber crumb |
| FR3118047B1 (en) | 2020-12-23 | 2022-12-30 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3118046B1 (en) | 2020-12-23 | 2022-12-30 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3118044B1 (en) | 2020-12-23 | 2022-12-30 | Michelin & Cie | RUBBER COMPOSITION |
| FR3118045B1 (en) | 2020-12-23 | 2022-12-30 | Michelin & Cie | RUBBER COMPOSITION |
| FR3123655B1 (en) | 2021-06-07 | 2023-04-28 | Michelin & Cie | CONVEYOR BELT COMPRISING A HIGHLY SATURATED ELASTOMER BASED COMPOSITION |
| FR3123654B1 (en) | 2021-06-07 | 2023-04-28 | Michelin & Cie | RUBBER COMPOSITION BASED ON HIGHLY SATURATED ELASTOMER AND BUTADIENE-STYRENE COMPOLYMER |
| FR3123920B1 (en) | 2021-06-15 | 2023-04-28 | Michelin & Cie | RUBBER COMPOSITION BASED ON COPOLYMER CONTAINING ETHYLENE UNITS AND DIENIC UNITS, AND POLYETHYLENE |
| FR3123919B1 (en) | 2021-06-15 | 2023-04-28 | Michelin & Cie | RUBBER COMPOSITION BASED ON COPOLYMER CONTAINING ETHYLENE UNITS AND DIENIC UNITS, AND POLYETHYLENE |
| FR3124514B1 (en) | 2021-06-25 | 2023-06-02 | Michelin & Cie | RUBBER COMPOSITION WITH IMPROVED RESISTANCE TO AGGRESSION |
| FR3129397B1 (en) | 2021-11-22 | 2023-11-10 | Michelin & Cie | Rubber composition |
| FR3129400B1 (en) | 2021-11-22 | 2023-11-10 | Michelin & Cie | Rubber composition |
| FR3129398A1 (en) | 2021-11-22 | 2023-05-26 | Compagnie Generale Des Etablissements Michelin | Rubber composition |
| FR3129399B1 (en) | 2021-11-22 | 2023-11-10 | Michelin & Cie | Rubber composition |
| FR3129396B1 (en) | 2021-11-22 | 2023-11-10 | Michelin & Cie | Rubber composition |
| FR3129401B1 (en) | 2021-11-22 | 2023-11-10 | Michelin & Cie | Rubber composition |
| FR3130281A1 (en) | 2021-12-10 | 2023-06-16 | Compagnie Generale Des Etablissements Michelin | ANTI-VIBRATION RUBBER COMPOSITION |
| FR3130807A1 (en) | 2021-12-16 | 2023-06-23 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
| FR3135723B1 (en) | 2022-05-17 | 2024-04-19 | Michelin & Cie | RUBBER COMPOSITION BASED ON A HIGHLY SATURATED ELASTOMER AND A POLAR LIQUID PLASTICIZER |
| FR3135722B1 (en) | 2022-05-17 | 2024-04-19 | Michelin & Cie | RUBBER COMPOSITION BASED ON A HIGHLY SATURATED ELASTOMER AND A LIQUID PLASTICIZER |
| FR3136473A1 (en) | 2022-06-14 | 2023-12-15 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
| FR3136768B1 (en) | 2022-06-20 | 2024-05-31 | Michelin & Cie | Diene rubber composition comprising a microsilica. |
| FR3136771B1 (en) | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3143035A1 (en) | 2022-12-08 | 2024-06-14 | Compagnie Generale Des Etablissements Michelin | Rubber composition |
| FR3143032A1 (en) | 2022-12-08 | 2024-06-14 | Compagnie Generale Des Etablissements Michelin | COMPOSITE FOR RUBBER ARTICLE |
| FR3143033A1 (en) | 2022-12-12 | 2024-06-14 | Compagnie Generale Des Etablissements Michelin | Tire for vehicle carrying heavy loads |
| FR3143034A1 (en) | 2022-12-13 | 2024-06-14 | Compagnie Generale Des Etablissements Michelin | Rubber composition |
| FR3143612A1 (en) | 2022-12-15 | 2024-06-21 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
| FR3143613A1 (en) | 2022-12-15 | 2024-06-21 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| US5109085A (en) * | 1990-08-27 | 1992-04-28 | Phillips Petroleum Company | Olefin polymerization process |
| JPH11171930A (en) * | 1997-12-16 | 1999-06-29 | Ube Ind Ltd | Composite elastomer and its production |
| FR2799468B1 (en) * | 1999-10-12 | 2006-04-28 | Michelin Soc Tech | CATALYTIC SYSTEM USABLE FOR THE COPOLYMERIZATION OF ETHYLENE AND A CONJUGATE DIENE, PROCESS FOR THE PREPARATION OF THIS CATALYTIC SYSTEM AND OF A COPOLYMER OF ETHYLENE AND A CONJUGATE DIENE |
-
2003
- 2003-10-13 CN CNA2007100042409A patent/CN101045770A/en active Pending
- 2003-10-13 RU RU2005114520/04A patent/RU2312870C2/en not_active IP Right Cessation
- 2003-10-13 AU AU2003286138A patent/AU2003286138A1/en not_active Abandoned
- 2003-10-13 CA CA002502345A patent/CA2502345A1/en not_active Abandoned
- 2003-10-13 KR KR1020057006637A patent/KR20050101157A/en active Search and Examination
- 2003-10-13 WO PCT/EP2003/011303 patent/WO2004035639A1/en active Application Filing
- 2003-10-13 CN CNB2003801033661A patent/CN100523023C/en not_active Expired - Lifetime
- 2003-10-13 EP EP03776864.5A patent/EP1554321B1/en not_active Expired - Lifetime
- 2003-10-13 JP JP2004544193A patent/JP5301073B2/en not_active Expired - Fee Related
- 2003-10-13 BR BR0315380-0A patent/BR0315380A/en not_active Application Discontinuation
-
2005
- 2005-04-15 US US11/106,619 patent/US7094854B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699171A (en) * | 2015-12-08 | 2018-10-23 | 米其林集团总公司 | 1,3- diene and ethylene or simple function or the distant pawl copolymer of α-monoolefine |
| CN108699187A (en) * | 2015-12-08 | 2018-10-23 | 米其林集团总公司 | The simple function or distant pawl copolymer of 1,3- butadiene and ethylene |
| CN108699187B (en) * | 2015-12-08 | 2020-12-22 | 米其林集团总公司 | Monofunctional or telechelic copolymers of 1, 3-butadiene and ethylene |
| CN108699171B (en) * | 2015-12-08 | 2021-09-03 | 米其林集团总公司 | Monofunctional or telechelic copolymers of 1, 3-dienes with ethylene or alpha-monoolefins |
| CN111212860A (en) * | 2017-10-19 | 2020-05-29 | 米其林集团总公司 | Block polymers having diene units and monoolefin units |
| CN111819209A (en) * | 2018-03-05 | 2020-10-23 | 株式会社普利司通 | Copolymer, method for producing copolymer, rubber composition, and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1554321B1 (en) | 2014-06-04 |
| US7094854B2 (en) | 2006-08-22 |
| AU2003286138A8 (en) | 2004-05-04 |
| AU2003286138A1 (en) | 2004-05-04 |
| WO2004035639A1 (en) | 2004-04-29 |
| JP2006503141A (en) | 2006-01-26 |
| CN100523023C (en) | 2009-08-05 |
| KR20050101157A (en) | 2005-10-20 |
| BR0315380A (en) | 2005-08-23 |
| EP1554321A1 (en) | 2005-07-20 |
| CA2502345A1 (en) | 2004-04-29 |
| JP5301073B2 (en) | 2013-09-25 |
| RU2312870C2 (en) | 2007-12-20 |
| US20050239639A1 (en) | 2005-10-27 |
| RU2005114520A (en) | 2005-11-10 |
| CN101045770A (en) | 2007-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1711292A (en) | Ethylene/butadiene copolymers, catalytic system and process for the synthesis thereof | |
| CN1125833C (en) | Dynamic Vulcanization of polymer blends from series reactors | |
| JP5538721B2 (en) | Lanthanide borohydride metallocene complex, catalyst system comprising the complex, polymerization process using the catalyst, and ethylene-butadiene copolymer obtained using the process | |
| WO2007054224A2 (en) | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method | |
| FR2799468A1 (en) | CATALYTIC SYSTEM USABLE FOR THE COPOLYMERIZATION OF ETHYLENE AND A CONJUGATE DIENE, PROCESS FOR THE PREPARATION OF THIS CATALYTIC SYSTEM AND OF A COPOLYMER OF ETHYLENE AND A CONJUGATE DIENE | |
| CN1109474A (en) | Metallocene catalysts with lewis acids and aluminum alkyls | |
| WO1995009172A1 (en) | Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer by using said catalyst | |
| JP2007501881A5 (en) | ||
| CN1364818A (en) | New olefine polymerization catalyst | |
| CN1555349A (en) | Method for alpha-olefin trimerization | |
| CN1239521C (en) | Transition metal catalysts for olefin polymerization | |
| CN101077879A (en) | Monodentate compound containing phenoxy, preparation method and application thereof | |
| CN1137157C (en) | Activating composition of metallocene matches in olefin catalytic copolymerization process | |
| CN110698513A (en) | Preparation of trihydroquinoline amine metal compound and application of trihydroquinoline amine metal compound in high-temperature solution polymerization of olefin | |
| CN1278265A (en) | Method for preparing fluvene metal complexes | |
| CN1329098A (en) | Polybutadiene and preparing method thereof | |
| CN101029096A (en) | Neutral non-bridged combined metal chromium catalyst and its use | |
| CN1103869A (en) | New halogenated complexes of lanthanides and their use in the polymerization of unsaturated monomers | |
| CN1922212A (en) | Preparation method of solid titanium catalyst for olefin polymerization | |
| CN1088588A (en) | The multipolymer of ethene and olefinic monomer, its preparation method and catalyzer | |
| CN1203096C (en) | Polymerization catalyst for unsaturated monomer, novel transition metal compound, and pdymerization method and copolymer using them | |
| CN1150215C (en) | Heteroleptic alkaline-earth metal compounds and methods for carrying out stereoselective anionic polymerization | |
| CN1245806A (en) | Catalyst based on metal fulvene compounding ingredient | |
| FR2893030A1 (en) | New ethylene butadiene copolymer comprises butadiene and 1,2-cyclohexane units | |
| CN1934144A (en) | Grafting of transition metal complexes on supports. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN Free format text: FORMER NAME: SOCIETE DE TECHNOLOGIE MICHELIN |
|
| CP01 | Change in the name or title of a patent holder |
Address after: French Clermont Ferrand Patentee after: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN Patentee after: MICHELIN RECHERCHE ET TECHNIQUE S.A. Patentee after: Total Petrochemical Institute Address before: French Clermont Ferrand Patentee before: Michelin Soc Tech Patentee before: MICHELIN RECHERCHE ET TECHNIQUE S.A. Patentee before: Total Petrochemical Institute |
|
| CX01 | Expiry of patent term |
Granted publication date: 20090805 |
|
| CX01 | Expiry of patent term |